CN1132503A - Method for preparing of mono or Di-2-substituted cyclopentanone - Google Patents
Method for preparing of mono or Di-2-substituted cyclopentanone Download PDFInfo
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- CN1132503A CN1132503A CN94193694A CN94193694A CN1132503A CN 1132503 A CN1132503 A CN 1132503A CN 94193694 A CN94193694 A CN 94193694A CN 94193694 A CN94193694 A CN 94193694A CN 1132503 A CN1132503 A CN 1132503A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/48—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation involving decarboxylation
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Abstract
The present invention provides a method for the preparation of mono or di_2-substituted cyclopentanone characterized in that it consists in performing in sequence four stages (a) to (d) which can be successively carried out, if desired, in the same reactor: (a) addition of alkyl acetoacetate to 1,3-butadiene, optionally 2-substituted; (b) the addition product formed is subjected to deacylation, following by an alkaline hydrolysis reaction and acidification to produce a carboxylic monacid having 6 carbon atoms in its main chain; (c) said monacid is subjected to hydroxycarbonylation to produce an alpha , omega -carboxylic diacid having 6 carbon atoms in its mains chain; and (d) said diacid is subjected to cyclizing decarboxylation. The invention is especially intended for the preparation of 2,2-dimethylcyclopentanone.
Description
The present invention relates to be used to prepare on the 2-position one replaces or the method for dibasic cyclopentanone.The present invention relates more specifically to prepare 2, the 2-cyclopentanone dimethyl.
Technical field of the present invention
Naphthenone (for example on the 2-position one replace or dibasic cyclopentanone) can be advantageously used for the intermediate of sterilant (benzylidene pyrryl methyl cycloalkane) in synthetic, and this series bactericidal agent is at EP-A-0, concrete narration is arranged in 378,953.
Purpose of the present invention
Though being used to prepare on the 2-position one replaces or the existing in the literature many reports of method of dibasic cyclopentanone (especially can be referring to J.Am.Chem.Soc., 60,2416-2419 (1938); Bull.acad.sci.URSS, Classe sci.Chim., (29-40), 489-493 (1947) and CA42,4536d; J.Org.Chem., 25,1841-1844 (1960); J.Am.Chem.Soc., 102 (1), 190-197 (1980); Organometallics, 7 (4), 936-945 (1988)), but needing really to have a kind of method, this method can be from that be easy to get and inexpensive raw material, operates with technical scale easily and need not adopt complex apparatus, makes the production of good cyclopentanone become possibility.
Had now found that the method that can arrive this purpose, this constitutes theme of the present invention just.
Description of the invention
The present invention relates to be used to prepare a replacement on the 2-position of following formula or the method for dibasic cyclopentanone:
Step (a) comprising:
* (a
1) make the 1,3-butadiene that on the 2-position, replaces arbitrarily of formula (II):
(R wherein
1Definition and above-mentioned formula (I) identical) react with the compound that has active methylene group of formula (III):
(wherein X represents R
6Or OR
6Group, R
5And R
6Can be identical or different, each expression contains the straight or branched alkyl of 1 to 6 carbon atom), this reaction is to carry out in the presence of catalyzer in aqueous medium, and this catalyzer comprises at least a water-soluble phosphine and at least a rhodium compound, obtains the reaction product of formula (IV):
Wherein, R
1, R
5Identical with in the definition of X and above-mentioned formula (I) and the formula (III),
* carry out (a then
2), by sedimentation, the water-soluble liquid phase that will contain catalyzer is separated with organic phase, and the reaction product of segregation type (IV) (this product is in organic phase) randomly can make reaction product obtain purifying by with the The suitable solvent extraction and/or by distillation then;
Step (b) comprising: the reaction product of use formula (IV), this product are from above-mentioned steps (a
2) in organic phase in obtain, be the form of crude product form or pure products, and:
* (b
1), if the compound of use formula (IV), wherein X represents the R6 group, then with this compound:
(b
1.1) carry out known processing by alcoholic solution with the alkali metal alkoxide that has made, make it carry out de-acyl reaction, obtain the reaction product of formula V:
R wherein
1And R
5Definition and above-mentioned formula (IV) in identical,
(b
1.2), carry out COOR after this reaction
5Acidification reaction is carried out in the alkaline hydrolysis of ester group then, and these react all with known method, carry out in same reaction medium, obtain the product of formula (VI):
R wherein
1Definition and above-mentioned formula (I) in identical,
* (b '
1), if the compound of use formula (IV), wherein X represents OR
6Group, then with this compound:
(b '
1.1), carry out COOR
5And COOR
6The basic hydrolysis of ester group,
(b '
1.2), after this reaction the carboxylate groups that generates is carried out the thermal decarboxylation reaction, carry out acidification reaction then, these react with known method, carry out in same reaction medium, obtain the product of formula (VI):
R wherein
1Definition and above-mentioned formula (I) in identical,
* (b then
2) water phase separated from organic phase, the segregation reaction product, the monocarboxylic acid of formula (VI) (this product is at aqueous phase) can make reaction product carry out purifying randomly by with the The suitable solvent extraction then;
Step (c): comprise the acid of use formula (VI), this product can be from above-mentioned steps (b
2) in the crude product form that obtains at aqueous phase, or the form of pure products, and:
* (c
1), according to first kind of possibility, use formic acid as the vehicle of water and CO and based on strong inorganic or organic acid catalyzer, make this compound carry out the hydroxy carbonyl reaction, obtain the reaction product of formula (VII):
R wherein
1Definition and above-mentioned formula (I) in identical,
* (c '
1), according to second kind of possibility, directly use CO pressure as the CO of 1MPa to 10MPa, water and based on strong inorganic or organic acid catalyzer, make this compound carry out the hydroxy carbonyl reaction, obtain the reaction product of formula (VII):
R wherein
1Definition and above-mentioned formula (I) in identical,
* (c then
2), make this compound precipitation by in reaction medium, adding water, the segregation reaction product, the dicarboxylic acid of formula (VII) then can be randomly by this diacid of recrystallization purifying;
Step (d): comprise the dicarboxylic acid of use formula (VII), this product can be from above-mentioned steps (c
2) in the crude product form that obtains of precipitation, or the form of pure products, and:
* (d
1), according to first kind of possibility, by with low-grade carboxylic acid's anhydride reactant, make diacid change into cyclic anhydride, in reaction, lose CO then
2, make this compound carry out the cyclisation decarboxylic reaction, obtain the cyclopentanone of needed formula (I),
* (d '
1), according to second kind of possibility, by in the presence of based on the catalyzer of following material, make diacid pyrolysis in water or gas phase, obtain the cyclopentanone of needed formula (I): (i) be selected from element Rb, Cs, V, Mo, B, Al, Ga, In, Tl, Sn, metal among Sb or the Bi or metalloid or derivatives thereof, perhaps (2i) phosphoric acid derivatives, the phosphoric acid of condensation or non-condensation, its proton is replaced or is replaced by ammonium ion by metal in above-mentioned (i) or the metallic cation the metalloid
* (d then
2), with the appropriate means reaction product of emanating.
As R
1Having of can mentioning of non-limiting example (outside the dehydrogenation): methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-or the tertiary butyl and corresponding alkoxyl group and phenyl, neighbour, or p-methylphenyl, xylyl and benzyl.
As R
5And R
6Having of can mentioning of non-limiting example: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-and the tertiary butyl.
Be preferably R
1Be methyl, and R
5And R
6(can be identical or different) be methyl and ethyl.
Therefore, a problem is, in the step (a) of method of the present invention, how formula (III) compound that contains active methylene group carries out addition reaction on the 4-carbon of the 1,3-butadiene of formula (II) (can randomly having substituting group on the 2-carbon).This reaction can be carried out with known method, especially as EP-A-0, is mentioned in 044,771 document, and the content of the document is hereby incorporated by reference; This reaction makes the adduct of the formula of obtaining (IV) become possibility, and this product is mainly to comprise following two kinds of mixture of isomers:
For used divinyl, carry out addition reaction by (preferably these conditions combine) under 1 to 8 the advantageous conditions below, the adduct that can obtain formula (IV) is (according to the definition of X, can be ketone ester or diester) the molar yield of excellence, this productive rate can reach 90%, even more than 90%: 1. the divinyl of every mole of formula (II) that replaces arbitrarily uses 1 to 1.5mol formula (III) to contain the compound of active methylene group; 2. X is R in the utilization structure
6Compound as the reactant that contains active methylene group of formula (III); 3. use the compound of the sodium, potassium, calcium, barium, ammonium, tetramethyl-ammonium and the tetraethyl-ammonium salt that are selected from (sulfophenyl) diphenylphosphine, two (sulfophenyl) Phenylphosphines and three (sulfophenyl) phosphine as the solubility phosphine; 4. use and be selected from rhodium oxide Rh
2O
3Rhodium chloride RhCl
3Bromination rhodium RhBr
3Rhodium sulfate Rh
2(SO
4)
3Rhodium nitrate Rh (NO
3)
3Rhodium acetate Rh (CH
3CO
2)
3Four rhodium carbonyls [Rh (CO)
4]
2Acetylacetonate trivalent rhodium; Chlorination (1, the 5-cyclooctadiene) rhodium [Rh (C
8H
12Cl]
2Or chlorination dicarbapentaborane rhodium [Rh (CO)
2Cl]
2Water-soluble cpds as rhodium compound; 5. the consumption of rhodium compound (the grammeatom numerical table with the used elemental rhodium of every 100mol divinyl shows) is for O.02 to 20; 6. the consumption of phosphine (mole number with used this compound of each grammeatom elemental rhodium is represented) is 1 to 10; 7. will contain alkali-metal alkali (for example sodium hydroxide, yellow soda ash or sodium bicarbonate) and add in the reaction medium, and be intended to improve reactive behavior, add-on is to add 0.01 to 3mol alkali in every premium on currency, forms the part of reaction medium composition; Temperature of reaction be 50 ℃ to 150 ℃ and keep for some time, the length of this time depend on selected temperature and can, for example, change in the scope of 2 hours (be reflected under 100 ℃ and carry out) to 5 hours (be reflected under 80 ℃ and carry out).
About actual used utensil in the addition reaction of step (a), more specifically can be with reference to above-mentioned document EP-A-0, the content in 044,771.
In the step (b) of the inventive method, get (b
1), what carry out is: the de-acyl reaction of the ketone ester compound of-formula (IV) comprises with hydrogen atom replacing removable COX (X=R wherein
6), obtain the ester of formula V, then-ester of described formula V carries out alkaline hydrolysis, makes the reaction medium acidifying then, displaces the carboxylic acid of required formula (VI) from its salt (generating on the spot).
In the step (b) of the inventive method, get (b '
1), what carry out is: the COOR in the diester of-formula (IV)
5And COOR
6The alkaline hydrolysis of two ester groups, generation is as the compound that contains two carboxy acid alkali's metal-salt groups of intermediate, then-the reaction medium acidifying after, one in these two carboxy acid alkali's metal-salt groups is carried out decarboxylation, and remaining carboxy acid alkali's metal-salt groups converted is carboxy CO OH, obtains the carboxylic acid of required formula (VI).
All these reactions can be used especially at Bull.Chem.Soc.Japan, and 52 (1), the known method of mentioning in 216-217 (1979) document is carried out, and its content is also incorporated by reference at this.
Consider the above [referring to step (a), operational condition 2], the most normal compound from the formula (IV) that exists with the ketone ester form of step (b) begins to carry out, and that is to say by using (b
1).
When the ketone ester of use formula (IV), react by (preferably these conditions combine) under 1 to 7 the favourable condition below, can obtain the molar yield of the excellence of formula (VI) carboxylic acid, this productive rate can reach 80%, even more than 80%: 1. use the alkoxide that derives from basic metal (for example sodium and potassium) and contain straight or branched primary monohydroxy-alcohol (for example methyl alcohol and ethanol) of 1 to 5 carbon atom to carry out de-acyl reaction.2. use the alcoholic solution of alkoxide, this solution makes in alcohol, can contain alcohol up to 20mol with respect to each mole alkoxide alkali in this solution, contains 5 to 15mol alcohol or rather; 3. the raw material ketone ester of every mole of formula (IV) uses 1 to 1.5mol alkoxide alkali; 4. normally what carry out corresponding to the boiling temperature of used alcohol, the time that reaction continues should be enough to remove (generating on the spot) R to de-acyl reaction
6-CO-G compound is as the criterion, in the structure of this compound, G represent used alkali metal alkoxide organic group (when alkali metal alkoxide is used, for example, CH
3During ONa, this G group is represented OCH
3); This reaction times is, for example, and 2 to 6 hours; 5. after de-acyl reaction is finished, that is to say and remove R
6After-CO-G the compound, carry out basic hydrolysis by the water that in reaction medium, adds with every 1mol alkali metal alkoxide alkali 10 to 30mol amounts; 6. basic hydrolysis normally carries out under corresponding to the reflux temperature of reaction mixture, and the time that reaction continues should be enough to remove the alcohol that exists in the described mixture by distillation and be as the criterion; 7. hydrolysis reaction is inorganic single acid by adding specified quantitative or polyacid (but can contain or oxygen-free, for example hydrochloric acid, nitric acid and sulfuric acid) the residual reacting mixture solution of acidifying, and making the pH value is about about 1 to 3 to make it completely.
About actual used utensil in de-acyl reaction and the basic hydrolysis, more specifically can be with reference to above-mentioned document Bull.Chem.Soc.Japan, 52 (1), the content among the 216-217 (1979).
In the step (c) of the inventive method, carboxy CO OH added to have substituent R
1The carbon atom of carboxylic acid of formula (VI) on.Should syntheticly require for every mole of total importing 1mol carbon monoxide (CO) and 1mol water of carboxylic acid for the treatment of functionalized formula (VI).
First kind of synthetic method is (corresponding to (c
1)) comprise and use formic acid as water and CO vehicle and adopt catalyzer based on strong acid; A kind of similar known response is arranged (especially referring to document New J.Chem. in the prior art, 1992,16,521-524, its content is hereby incorporated by reference), but the substrate that has the monocarboxylic acid compound structure that never is used for formula (VI) is in the hope of making the dicarboxylic acid of formula (VII).
Another kind of synthetic method (good especially, corresponding to (c '
1)) comprise adding and depress in the presence of based on the catalyzer of strong acid, directly react with CO; A kind of similar known reaction is also arranged (especially referring to document Russian Chemical Reviews in the prior art, 58 (2), 117-137 (1989), its content is also incorporated by reference at this), but never used the substrate that has the monocarboxylic acid compound structure of formula (VI).
For (c '
1) (being the most frequently used step), when the monocarboxylic acid of use formula (VI), react by (preferably these conditions combine) under 1 to 7 the advantageous conditions below, can obtain the molar yield of the dicarboxylic acid of excellent formula (VII), this productive rate can reach 85%, even more than 85%: 1. excessive greatly down at CO, in a suitable reactor, react, the starting compound that is to say every mole of formula (VI) for the treatment of hydroxy carbonyl adds under the required pressure of CO gas between 1MPa to 10MPa corresponding to the CO greater than the amount of 2mol; 2. in when beginning reaction, the essential all components that exists in the attentive response device; 3. use strong inorganic or organic list or polyacid (but can contain or oxygen-free) as catalyzer, at least one acid functional group wherein (when having many) has and is less than or equal to ionization constant pKa ' in 3 the water, for example: from the mineral acid of hydrochloric acid, sulfuric acid, phosphoric acid or tetra-sodium; Organic acid from organic sulfonic acid (especially tosic acid, methylsulfonic acid or naphthene sulfonic acid), organic phospho acid (especially an alkyl or an arylphosphonic acid, for example methyl-phosphorous acid or phenyl-phosphonic acid) or the strong carboxylic acid of many halos (for example dihalo and three halos, especially chlorine and fluoro acetate or propionic acid).The strong acid of particularly suitable is sulfuric acid; 4. when carrying out the hydroxy carbonyl reaction, the raw material carboxylic acid of every mole of formula (VI) uses 1 to 15mol water and 1O to 50H
+Ion; 5. the water and the strong acid that react required import with reaction medium with the form that concentrates strong acid aqueous solution, and wherein the weight concentration of pure acid and amount are specific, so that can import the water and the requisite number purpose H of aequum
+Ion; 6. use dense strong acid aqueous solution, wherein the concentration of pure acid (weight) is 90 to 98%; 7. temperature of reaction, and is retained to CO always and absorbs and to stop to 100 ℃ from room temperature (20 ℃).
For another (c
1) conversion step, can be below under 1 to 6 the advantageous conditions (preferably these conditions are interosculated) react: 1. by with formic acid (conversion step c
1.1) or mixture (the conversion step c of the raw material carboxylic acid of formic acid and formula (VI)
1.2) add in the reactor that contains following material and react: for conversion step c
1.1, contain the raw material carboxylic acid of strong acid catalyst and formula (VI); Perhaps for conversion step c
1.2, only contain strong acid catalyst; 2. the consumption of formic acid (representing with respect to the mole number of the carboxylic acid of one mole of formula (VI) with this compound) is 1 to 4mol; 3. use corresponding to top conversion step (c '
1) provide the compound of definition as catalyzer in the condition 3 of reacting; 4. strong acid catalyst uses with pure state or with the form of concentrated aqueous solutions, and wherein the concentration of pure acid (weight) is at least 95%; 5. the consumption of strong acid catalyst is (with the H of the raw material carboxylic acid of every mole of formula (VI)
+Numerical table shows) be 5 to 40H
+Ion; 6. temperature of reaction, and kept 3 hours to 6 hours according to temperature value to 100 ℃ from room temperature (20 ℃).
About utensil actual used in the hydroxy carbonyl reaction, more specifically can be with reference to chemical book of reference, also can be with reference to above-mentioned document Russian Chemical Reviews, 58 (2), 117-137 (1989) and New J.Chem., 1992,16,521-524.
In the step (d) of the inventive method, the dicarboxylic acid of formula (VII) carries out the cyclopentanone that cyclisation obtains formula (I).
First kind of synthetic method is (corresponding to (d
1)) comprise, by with low-grade carboxylic acid's anhydride reactant, diacid is changed into cyclic anhydride, under Temperature Influence, in reaction process, lose CO then
2A kind of similar reaction known in the state of the art (especially referring to document Compt.rend., 142,1084-1085 (1906) and Compt.rend., 144,1356-1358 (1907), its content is hereby incorporated by reference).
Another kind of synthetic method (be particularly useful for this, corresponding to (d '
1)) comprise and make diacid in liquid phase or gas phase, in the presence of special catalyst, carry out pyrolytic reaction; A kind of similar known response is also arranged (especially referring to document Bull.acad.sci.URSS in the prior art, classesci.chim., (29-40), 489-493 (1947) and J.Org.Chem., 25,1841-1844, (1960)), but wherein do not mention said use specific catalyst here.
For (d '
1), when the dicarboxylic acid of use formula (VII), carry out pyrolytic reaction by (preferably these conditions are interosculated) under 1 to 6 the advantageous conditions below, obtain the molar yield of the required cyclopentanone of excellent formula (I), this productive rate can reach 75%, even more than 75%: 1. in liquid phase, carry out the cyclisation decarboxylic reaction, that is to say reaction in the presence of reaction solvent (mixture of organic solvent or multiple organic solvent), described solvent is inert to the raw material dicarboxylic acid with the cyclic ketones that obtains, and has 200 ℃ to 500 ℃ high boiling point temperature.Specific examples as the organic solvent that is suitable for can should be mentioned that especially: paraffinic (for example decane, undecane, dodecane or the tetradecane); Aromatic hydrocarbons (for example dimethylbenzene, cumene or contain petroleum fractions, especially Solvesso class (a kind of high solvent of aromatic hydrocarbons amount that the contains) cut of alkylbenzene mixture); The senior ester class (for example octyl phthalate) of senior ester class of mineral acid (for example tricresyl phosphate (toluene ester)) or carboxylic acid; Aromatics ethers (for example phenyl ether or dibenzyl ether); Paraffinic hydrocarbons and/or cycloalkanes oils or oily distillatory resistates; 2. the concentration of the raw material dicarboxylic acid of the formula (VII) that is generated by raw material diacid, catalyzer and organic solvent in reactant is generally 10 to 50% of reactant weight; 3. material is as catalyzer below using :-type (i), the metal of rubidium, caesium, vanadium, molybdenum, boron, aluminium, gallium, indium, thallium, tin, antimony or bismuth or metalloid form; List or double oxide or list or double-hydroxide form; Single or two inorganic salt form (for example nitrate, vitriol, oxysulfate, halogenide, contain oxyhalogenation thing, silicate or carbonate); Perhaps single or two organic salt forms (for example acetylacetonate, alkoxide (as methoxide or b-oxide), or carboxylate salt (as acetate or oxalate)).As the specific examples of (i) catalyzer that is suitable for, to mention following catalyzer especially: sodium tetraborate or potassium tetraborate; Stannic oxide; Sodium stannate or potassium stannate; Bismuth carbonate, cesium carbonate or rubidium carbonate; Molybdenum oxide, aluminum oxide, Indium sesquioxide or weisspiessglanz; Perhaps thallium acetate;-type (2i), phosphoric acid salt or condensed phosphate, pyrophosphate salt or Tripyrophosphoric acid salt, positively charged ion especially comes comfortable Bulletin de la Societe Chimique deFrance in its structure, the positively charged ion or the ammonium ion of 1A (except that rubidium and caesium), 2A or 3B family element in the periodic classification that No.1 (1966) announces.As the specific examples of (2i) catalyzer that is suitable for, to mention following catalyzer especially: sodium phosphate or potassiumphosphate, trisodium phosphate or potassium pyrophosphate, Tri sodium Phosphate or tri-potassium phosphate, perhaps five sodium phosphates or five potassiumphosphates; 4. catalyst consumption (using the grammeatom numerical table corresponding to the metallic cation of every 100mol dicarboxylic acid to show) is 0.1 to 30%, more properly is 5 to 20%; 5. carry out the cyclisation decarboxylic reaction under 200 ℃ to 300 ℃ temperature, this temperature may be selected to the reflux temperature that equals reaction mixture; 6. remove (in case generation) cyclic ketones, carbon dioxide and water carrying out the cyclisation decarboxylic reaction by distillation, when reaction finishes, from overhead product, reclaim cyclic ketones with the ordinary method (especially by sedimentation or crystallization) in present technique field.
The following examples (not meaning that restriction) are used to illustrate the present invention, and how explanation the present invention is applied in the practice.
Embodiment 1
The process of carrying out of step (a) in present embodiment explanation the inventive method.
Article below in the stainless steel autoclave of crossing with nitrogen purge in advance, importing successively :-93.6mg[Rh (1, the 5-cyclooctadiene) Cl]
2, promptly 3.8 * 10
-4The grammeatom elemental rhodium ,-1.208g (11.4 * 10
-3Mol) Na
2CO
3,-2.736g contains the sodium-salt aqueous solution of three (sulfo group benzene) phosphine of 30% (weight) following formula:
The i.e. described phosphine of 14.4 * 10-4mol ,-80ml be through the distilled water of the nitrogen bubble degassing, the new isoprene that steams of-34g (0.50mol), and-71.8g (0.62mol) methyl acetoacetate.
After autoclave cuts out, make nitrogen pressure reach 2 * 10 adding automatically to depress
5Pa also heated 2 hours under 100 ℃.
After the cooling, with the material decant in the autoclave to separating funnel with water phase separated and organic phase.The aqueous phase of collecting contains catalyzer, and upper organic phase contains the adduct of required formula (IV) in (not containing catalyzer).
Wash isolating organic phase with the 20ml salt brine solution.With 50ml ethyl acetate extraction water, then with the washing of 20ml salt brine solution.Merge organic phase, use anhydrous Na then
2SO
4Dry.Filter Na
2SO
4Afterwards, under reduced pressure boil off ethyl acetate, under reduced pressure distill (70-72 ℃ of the head product that obtain with purifying; 3 * 10
2Pa), obtain the 91.14g colourless liquid,, wherein contain the ketone ester of 99% (weight) following formula through NMR, mass spectrum, IR and gas chromatographic analysis:
Molar yield corresponding to used isoprene is 98%.
Embodiment 2
The process of carrying out of step (b) in present embodiment explanation the inventive method.
In the 1 liter of three neck round-bottomed flask that cleaned with argon gas in advance and mechanical stirrer, thermometer, 250ml dropping funnel and distillation column are housed, import the 600ml anhydrous methanol.
The sodium that 27.6g (1.20mol) is shredded progressively imports in this round-bottomed flask then.After all sodium reactions were finished, the ketone ester of preparation added during about 10 minutes among 179.2g (0.974mol) embodiment 1, and made the solution that so obtains reach boiling point.Boil off methyl acetate (generating on the spot) wherein, and the part methyl alcohol that exists in the reaction medium.This distillation procedure need heat 3 hours.
At the terminal point of this time, progressively add 400ml distilled water, continue distillation simultaneously, to remove remaining methyl alcohol in the reaction medium.
After all methyl alcohol is all removed, make remaining reactant cooling, and wash with the 100ml hexanaphthene.Use H then
2SO
4Acidifying makes the pH value reach 2 through settlement separate water.
By sedimentation, the carboxylic acid of required formula (VI) separates automatically separates out.Aqueous phase extracted twice immediately, uses 100mlCH at every turn
2Cl
2Merge organic phase, use anhydrous Na then
2SO
4Dry.Filter Na
2SO
4Afterwards, under reduced pressure boil off CH
2Cl
2, under reduced pressure distill (70-74 ℃ of the head product that obtain with purifying; 3 * 10
2Pa), obtain the 108.3g colourless liquid,, wherein contain the carboxylic acid of 95% (weight) following formula through NMR, IR and vapor phase stratographic analysis:
Molar yield corresponding to used ketone ester is 82.5%.
Embodiment 3
The process of carrying out of step (c) in present embodiment explanation the inventive method.
Adding the concentrated sulfuric acid aqueous solution that 358.7g contains the pure acid of 95% (weight) in the 250ml three neck round-bottomed flasks that mechanical stirrer, thermometer and 50ml dropping funnel are housed (is 6.95H
+Ion and 0.997mol water).
Under agitation slowly import the carboxylic acid of preparation among 32g (0.25mol) embodiment 2 then, simultaneously temperature is remained on about 5 ℃.The solution decant that will so obtain then is to the autoclave that contains interior tantalum lining, and this autoclave stirs under the CO pressure of room temperature (20 ℃) and 5MPa.
After contacting 23 hours with CO, reactant is slowly imported in the water that remains on about 10 ℃.By filtering to isolate solid sediment, use the 50ml cold water washing then.After the drying, obtain the 39.2g white solid,, wherein contain the dicarboxylic acid of 92.5% (weight) following formula through NMR, IR and HPLC stratographic analysis:
Dilute remaining filtrate with 1 premium on currency, and kept 12 hours: can additional separation go out the required dicarboxylic acid of 3.17g pure state like this at 4 ℃.
Corresponding to the total molar yield of the dicarboxylic acid of used monocarboxylic acid is 90.8%.Embodiment 4
The process of carrying out of step (d) in present embodiment explanation the inventive method.
To heating system, mechanical stirrer, Vigreux type distillation column are housed and by the 50ml three neck round-bottomed flasks of solidified carbon dioxide refrigerative receptor in add 18.6g diphenyl ether (solvent), 5g (28.7 * 10
-3Mol) among the embodiment 3 preparation 2,2-dimethyl hexanodioic acid and 1.056g molecular formula are Na
2B
4O
710H
2The sodium tetraborate of O (promptly 5.6 * 10
-3Grammeatom sodium positive ion).
Under agitation, with reactant heating 15 minutes, until the reflux temperature that reaches solvent for use, this temperature was 250 ℃.Temperature is remained on 250 ℃ then, the cyclic ketones that distillation generates to by in the solidified carbon dioxide refrigerative collector until having steamed; This operation continues 1 hour 35 minutes.
Collect the 6.357g distillate, wherein contain the cyclic ketones of the following formula of generation:
Water and phenyl ether.Water is absorbed in the anhydrous sodium sulphate.Filter and use CH
2Cl
2After the drip washing, use CH
2Cl
2Make distillate reach 100ml, with the cyclopentanone dimethyl in the vapor-phase chromatography employing marker method analytical solution.
In distillation residue, add 20ml methylene dichloride, water and sodium hydroxide mixture (60/40, volume) 20ml extracting twice; The unconverted dimethyl hexanodioic acid that contains with HPLC chromatography analysis aqueous phase.
The result who obtains is as follows :-through gpc analysis, molar yield corresponding to the cyclopentanone dimethyl of used dicarboxylic acid is: 80%, the molar yield of-dicarboxylic acid is: 87% ,-corresponding to the molar yield of the cyclopentanone dimethyl of the dicarboxylic acid that transforms be: 92%.
Claims (26)
1. be used to prepare a replacement on the 2-position of following formula or the method for dibasic cyclopentanone:
R wherein
1Expression: hydrogen atom; The straight or branched alkyl or the alkoxyl group that contain 1 to 4 carbon atom; Or be formula (R
2)
p-phenyl-(CR
3R
4-)
qGroup, R wherein
2For containing the straight or branched alkyl of 1 to 3 carbon atom, R
3And R
4Can be identical or different, represent hydrogen atom separately or contain the straight or branched alkyl of 1 to 3 carbon atom, p and q are integer, and they can be identical or different, and its scope is 0 to 3; Described method is characterised in that it comprises following (a) that carry out continuously to (d) four steps, and if desired, these steps can be carried out in same reactor successively:
Step (a) comprising:
* (a
1), make the 1,3-butadiene that on the 2-position, replaces arbitrarily of formula (II):
(R wherein
1Definition and above-mentioned formula (I) identical) with the compound effect that has active methylene group of formula (III):
(wherein X represents R
6Or OR
6Group, R
5And R
6Can be identical or different, each expression contains the straight or branched alkyl of 1 to 6 carbon atom), this reaction is to carry out in the presence of catalyzer in aqueous medium, and this catalyzer comprises at least a water-soluble phosphine and at least a rhodium compound, obtains the reaction product of formula (IV):
Wherein, R
1, R
5Identical with in the definition of X and above-mentioned formula (I) and the formula (III),
* (a then
2), by sedimentation, the water-soluble liquid phase that will contain catalyzer is separated with organic phase, and the reaction product of segregation type (IV) (this product is in organic phase) randomly can make reaction product carry out purifying by with The suitable solvent extraction and/or distillation then;
Step (b) comprises the reaction product of use formula (IV), and this product can be from above-mentioned steps (a
2) in the crude product form that in organic phase, obtains or the form of pure products, and:
* (b
1), if the compound of use formula (IV), wherein X represents R
6Group then makes this compound:
(b
1.1), carry out known processing by alcoholic solution with the alkali metal alkoxide that has made, make it carry out de-acyl reaction, obtain the reaction product of formula V:
R wherein
1And R
5Definition and above-mentioned formula (IV) in identical,
(b
1.2), carry out COOR after this reaction
5The basic hydrolysis of ester group carries out acidification reaction then, and these react with known method, carry out in same reaction medium, obtain the product of formula (VI):
R wherein
1Definition and above-mentioned formula (I) in identical,
* (b '
1), if the compound of use formula (IV), wherein X represents OR
6Group then makes this compound:
(b '
1.1), carry out COOR
5And COOR
6The basic hydrolysis of ester group,
(b '
1.2), after this reaction, one of carboxylate groups of generating is carried out the thermal decarboxylation reaction, carry out acidification reaction then, these react with known method, carry out in same reaction medium, obtain the product of formula (VI):
R wherein
1Definition and above-mentioned formula (I) in identical,
* (b then
2), with organic phase and aqueous phase separation, the segregation reaction product, the monocarboxylic acid of formula (VI) (this product is at aqueous phase) randomly can make reaction product carry out purifying by with the The suitable solvent extraction then;
Step (c) comprises the acid of use formula (VI), and this product can be from above-mentioned steps (b
2) in the form of the crude product that obtains at aqueous phase or the form of pure products, and:
* (c
1), according to first kind of possibility, use formic acid as the vehicle of water and CO and based on strong inorganic or organic acid catalyzer, make this compound carry out the hydroxy carbonyl reaction, obtain the reaction product of formula (VII):
* (c '
1), according to second kind of possibility, directly use CO pressure as the CO of 1MPa to 10MPa, water and based on strong inorganic or organic acid catalyzer, make this compound carry out the hydroxy carbonyl reaction, obtain the reaction product of formula (VII):
R wherein
1Definition and above-mentioned formula (I) in identical,
* (c then
2), make this compound precipitation by in reaction medium, adding water, the segregation reaction product, the dicarboxylic acid of formula (VII) then can be randomly by this diacid of recrystallization purifying;
Step (d) comprises the dicarboxylic acid of use formula (VII), and it can be from above-mentioned steps (c
2) the middle form of the crude product that obtains or the form of pure products of precipitating, and:
* (d
1), according to first kind of possibility, by with low-grade carboxylic acid's anhydride reactant, make diacid change into cyclic anhydride, in reaction, lose CO then
2, make this compound carry out the cyclisation decarboxylic reaction, obtain the cyclopentanone of needed formula (I),
* (d '
1), according to second kind of possibility, by in the presence of based on the catalyzer of following material, make diacid pyrolysis in water or gas phase, obtain the cyclopentanone of needed formula (I): (i) be selected from Rb, Cs, V, Mo, B, Al, Ga, In, Tl, Sn, metal among Sb or the Bi or metalloid element or derivatives thereof, perhaps (2i) phosphoric acid derivatives, the phosphoric acid of condensation or non-condensation, its proton is replaced or is replaced by ammonium ion by metal in above-mentioned (i) or the metallic cation the metalloid
* (d then
2), with the appropriate means reaction product of emanating.
2. the method for claim 1 is characterized in that comprising following (a) that carry out continuously to (d) four steps, and if desired, these steps can be carried out in same reactor successively:
Step (a) comprising:
* (a
1), make the 1,3-butadiene that on the 2-position, replaces arbitrarily of formula (II):
(R wherein
1Definition and above-mentioned formula (I) identical) with the compound effect that has active methylene group of formula (III):
(wherein X represents R
6Group, R
5And R
6Can be identical or different, each expression contains the straight or branched alkyl of 1 to 6 carbon atom), this reaction is to carry out in the presence of catalyzer in aqueous medium, and this catalyzer comprises at least a water-soluble phosphine and at least a rhodium compound, obtains the reaction product of formula (IV):
Wherein, R
1, R
5Identical with in the definition of X and above-mentioned formula (I) and the formula (III),
* (a then
2), by sedimentation, the water-soluble liquid phase that will contain catalyzer is separated with organic phase, and the reaction product of segregation type (IV) (this product is in organic phase) randomly can make reaction product carry out purifying by with The suitable solvent extraction and/or distillation then;
Step (b) comprises the reaction product of use formula (IV), and this product can be from above-mentioned steps (a
2) in the crude product form that from organic phase, obtains or the form of pure products, and:
* (b
1), make this compound:
(b
1.1) carry out known processing by alcoholic solution with the alkali metal alkoxide that has made, make it carry out de-acyl reaction, obtain the reaction product of formula V:
R wherein
1And R
5Definition and above-mentioned formula (IV) in identical,
(b
1.2) carry out COOR after this reaction
5The basic hydrolysis of ester group carries out acidification reaction then, and these react with known method, carry out in same reaction medium, obtain the product of formula (VI):
R wherein
1Definition and above-mentioned formula (I) in identical,
* (b then
2), with organic phase and aqueous phase separation, the segregation reaction product, the monocarboxylic acid of formula (VI) (this product is at aqueous phase) randomly can make reaction product carry out purifying by with the The suitable solvent extraction then;
Step (c) comprises the acid of use formula (VI), and it can be from above-mentioned steps (b
2) in the crude product form that obtains at aqueous phase or the form of pure products, and:
* (c '
1), directly use CO pressure as the CO of 1MPa to 10MPa, water and based on strong inorganic or organic acid catalyzer, make this compound carry out the hydroxy carbonyl reaction, obtain the reaction product of formula (VII):
R wherein
1Definition and above-mentioned formula (I) in identical,
* (c then
2), make this compound precipitation by in reaction medium, adding water, the segregation reaction product, the dicarboxylic acid of formula (VII) then randomly can be by this diacid of recrystallization purifying;
Step (d) comprises the dicarboxylic acid of use formula (VII), and it can be from above-mentioned steps (c
2) the middle form of the crude product that obtains or the form of pure products of precipitating, and:
* (d '
1), by in the presence of based on the catalyzer of following material, make diacid pyrolysis in water or gas phase, obtain the cyclopentanone of needed formula (I): (i) be selected from metal or metalloid element or derivatives thereof among Rb, Cs, V, Mo, B, Al, Ga, In, Tl, Sn, Sb or the Bi, perhaps (2i) phosphoric acid derivatives, the phosphoric acid of condensation or non-condensation, its proton is replaced or is replaced by ammonium ion by metal in above-mentioned (i) or the metallic cation the metalloid
* (d then
2), with the appropriate means reaction product of emanating.
3. method as claimed in claim 1 or 2 is characterized in that R
1Corresponding to methyl, and R
5And R
6Can be identical or different, corresponding to methyl and ethyl.
4. as claim 2 or 3 described methods, it is characterized in that in step (a) that every mole can randomly substituted formula (II) divinyl be used 1 to 1.5mol formula (III) compound that contains active methylene group.
5. as any one described method in the claim 2 to 4, it is characterized in that in step (a), use a kind of compound in sodium, potassium, calcium, barium, ammonium, tetramethyl-ammonium and the tetraethyl-ammonium salt be selected from (sulfophenyl) diphenylphosphine, two (sulfophenyl) Phenylphosphines and three (sulfophenyl) phosphine as the solubility phosphine.
6. as any one described method in the claim 2 to 5, it is characterized in that in step (a), use to be selected from rhodium oxide Rh
2O
3Rhodium chloride RhCl
3Bromination rhodium RhBr
3Rhodium sulfate Rh
2(SO
4)
3Rhodium nitrate Rh (NO
3)
3Rhodium acetate Rh (CH
3CO
2)
3Four rhodium carbonyls [Rh (CO)
4]
2Acetylacetonate trivalent rhodium; Chlorination (1, the 5-cyclooctadiene) rhodium [Rh (C
8H
12) Cl]
2Or chlorination dicarbapentaborane rhodium [Rh (CO)
2Cl]
2A kind of water-soluble cpds as rhodium compound.
7. as any one described method in the claim 2 to 6, it is characterized in that in step (a) that the consumption of rhodium compound (the grammeatom numerical table with the used elemental rhodium of every 100mol divinyl shows) is 0.02 to 20.
8. as any one described method in the claim 2 to 7, it is characterized in that in step (a) that the consumption of phosphine (mole number with used this compound of a grammeatom elemental rhodium is represented) is 1 to 10.
9. as any one described method in the claim 2 to 8, it is characterized in that in step (a) that temperature of reaction is 50 ℃ to 150 ℃.
10. as any one described method in the claim 2 to 9, it is characterized in that in step (b), use the alkoxide that derives from basic metal and the straight or branched uncle monohydroxy-alcohol that contains 1 to 5 carbon atom to carry out de-acyl reaction.
11., it is characterized in that in step (b) that the raw material ketone ester of every mole of formula (IV) uses 1 to 1.5mol alkoxide alkali to carry out de-acyl reaction as any one described method in the claim 2 to 10.
12., it is characterized in that in step (b) that de-acyl reaction is to carry out in the boiling temperature corresponding to used alcohol as any one described method in the claim 2 to 11, the time that reaction continues should can be removed (generating on the spot) R with foot
6-CO-G compound is as the criterion, and in the structure of this compound, G represents the organic group of used alkali metal alkoxide.
13. as any one described method in the claim 2 to 12, it is characterized in that in step (b), after de-acyl reaction is finished, carry out basic hydrolysis by the water that in reaction medium, adds by every 1mol alkali metal alkoxide alkali use 10 to 30mol.
14., it is characterized in that in step (b) that basic hydrolysis is to carry out as any one described method in the claim 2 to 13 under corresponding to the reflux temperature of reaction mixture.
15. as any one described method in the claim 2 to 14, it is characterized in that in step (c), use strong inorganic or organic list or polyacid (but can contain or oxygen-free) as catalyzer, at least one acid functional group wherein (when having many) has and is less than or equal to ionization constant pK in 3 the water
a
16., it is characterized in that in step (c) that hydroxy carbonyl reaction is that the raw material carboxylic acid by every mole of formula (VI) uses 1 to 15mol water and 10 to 50H as any one described method in the claim 2 to 15
+Ion carries out.
17. as any one described method in the claim 2 to 16, it is characterized in that in step (c), water that the hydroxy carbonyl reaction is required and strong acid import in the reaction medium with the form of dense strong acid aqueous solution together, wherein the weight concentration of pure acid and amount are specific, so that import the water and the requisite number purpose H of aequum
+Ion.
18., it is characterized in that the concentration (weight) of pure acid in the used spissated strong acid aqueous solution is 90 to 98% as any one described method in the claim 2 to 17.
19., it is characterized in that in step (c) that the hydroxy carbonyl temperature of reaction is to 100 ℃ from room temperature (20 ℃) as any one described method in the claim 2 to 18.
20. as any one described method in the claim 2 to 19, it is characterized in that in step (d), in liquid phase, carry out the cyclisation decarboxylic reaction, that is to say reaction in the presence of reaction solvent (mixture of organic solvent or multiple organic solvent), described solvent is inert to the raw material dicarboxylic acid with the cyclic ketones that obtains, and respectively has 200 ℃ to 500 ℃ high boiling point temperature.
21. method as claimed in claim 20 is characterized in that reaction solvent is selected from paraffinic, for example decane, undecane, dodecane or the tetradecane; Aromatic hydrocarbons is dimethylbenzene, cumene or contain the petroleum fractions of alkylbenzene mixture for example; The senior ester class of mineral acid, for example senior ester class of tricresyl phosphate (toluene ester) or carboxylic acid, for example octyl phthalate; Aromatics ethers, for example phenyl ether or dibenzyl ether; Paraffinic hydrocarbons and/or cycloalkanes oils or oily distillatory resistates.
22., it is characterized in that in step (d) that the concentration of the raw material dicarboxylic acid of the formula (VII) that is generated by raw material diacid, catalyzer and organic solvent is 10 to 50% of reactant weight as any one described method in the claim 2 to 21 in reactant.
23. as any one described method in the claim 2 to 22, it is characterized in that in step (d), material is as catalyzer below using :-type (i), the metal of rubidium, caesium, vanadium, molybdenum, boron, aluminium, gallium, indium, thallium, tin, antimony or bismuth or metalloid form; The form of list or double oxide or list or double-hydroxide; The form of single or two inorganic salt, for example nitrate, vitriol, oxysulfate, halogenide, contain oxyhalogenation thing, silicate or carbonate; The form of perhaps single or two organic salts, acetylacetonate for example, alkoxide, or carboxylate salt.-type (2i), phosphoric acid salt or condensed phosphate, pyrophosphate salt or Tripyrophosphoric acid salt, positively charged ion is from Bulletin de la Soci é t é Chimique de France in its structure, the positively charged ion or the ammonium ion of 1A (except that rubidium and caesium), 2A or 3B family element in the periodic classification that No.1 (1966) announces.
24., it is characterized in that in step (d) that catalyst consumption (using the grammeatom numerical table corresponding to the metallic cation of every 100mol dicarboxylic acid to show) is 0.1 to 30% as any one described method in the claim 2 to 23.
25. as any one described method in the claim 2 to 24, it is characterized in that in step (d), the cyclisation decarboxylic reaction is in 200 ℃ to 300 ℃ temperature range, equal to carry out under the reflux temperature of reaction mixture, remove (once what generate) cyclic ketones, carbon dioxide and water by distillation.
26. be used to prepare the method for the dicarboxylic acid of following formula:
Make this compound precipitation by add water in reaction medium then, segregation type (VII) reaction product then randomly can be by this diacid of recrystallization purifying.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9312153A FR2710908B1 (en) | 1993-10-07 | 1993-10-07 | Process for the preparation of cyclopentanone mono- or di-substituted in position 2. |
| FR93/12153 | 1993-10-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1132503A true CN1132503A (en) | 1996-10-02 |
Family
ID=9451769
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94193694A Pending CN1132503A (en) | 1993-10-07 | 1994-10-04 | Method for preparing of mono or Di-2-substituted cyclopentanone |
Country Status (14)
| Country | Link |
|---|---|
| EP (1) | EP0722432A1 (en) |
| JP (1) | JPH09503219A (en) |
| KR (1) | KR960704829A (en) |
| CN (1) | CN1132503A (en) |
| AU (1) | AU675367B2 (en) |
| BR (1) | BR9407734A (en) |
| CA (1) | CA2173618A1 (en) |
| CZ (1) | CZ100796A3 (en) |
| FI (1) | FI961553A (en) |
| FR (1) | FR2710908B1 (en) |
| HU (1) | HUT74481A (en) |
| IL (1) | IL111166A0 (en) |
| WO (1) | WO1995009830A1 (en) |
| ZA (1) | ZA947879B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086858A (en) * | 2012-12-30 | 2013-05-08 | 浙江工业大学 | Synthetic method of 3-methyl-cyclopentanone |
| CN110981710A (en) * | 2019-11-26 | 2020-04-10 | 万华化学集团股份有限公司 | Method for synthesizing methyl heptenone from isoprene |
| CN112010744A (en) * | 2019-05-29 | 2020-12-01 | 武汉臻智生物科技有限公司 | Farnesyl acetone and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3163383D1 (en) * | 1980-07-10 | 1984-06-07 | Rhone Poulenc Sante | Process for the selective addition of a compound having an activated carbon atom to a substituted conjugated diene |
| US4788333A (en) * | 1985-01-07 | 1988-11-29 | E. I. Du Pont De Nemours And Company | Hydrocarboxylation of unsaturated carboxylic acids to linear dicarboxylic acids |
| DE3622012A1 (en) * | 1986-07-01 | 1988-01-07 | Basf Ag | METHOD FOR PRODUCING CYCLIC KETONES |
| DE3638005A1 (en) * | 1986-11-07 | 1988-05-11 | Basf Ag | METHOD FOR PRODUCING CYCLOPENTANONE |
| DE3730185A1 (en) * | 1987-09-09 | 1989-03-23 | Basf Ag | METHOD FOR PRODUCING CYCLOPENTANONE |
-
1993
- 1993-10-07 FR FR9312153A patent/FR2710908B1/en not_active Expired - Fee Related
-
1994
- 1994-10-04 CZ CZ961007A patent/CZ100796A3/en unknown
- 1994-10-04 IL IL11116694A patent/IL111166A0/en unknown
- 1994-10-04 WO PCT/FR1994/001157 patent/WO1995009830A1/en not_active Application Discontinuation
- 1994-10-04 AU AU79958/94A patent/AU675367B2/en not_active Ceased
- 1994-10-04 JP JP7510645A patent/JPH09503219A/en active Pending
- 1994-10-04 HU HU9600905A patent/HUT74481A/en unknown
- 1994-10-04 CN CN94193694A patent/CN1132503A/en active Pending
- 1994-10-04 CA CA002173618A patent/CA2173618A1/en not_active Abandoned
- 1994-10-04 BR BR9407734A patent/BR9407734A/en not_active Application Discontinuation
- 1994-10-04 EP EP94931058A patent/EP0722432A1/en not_active Ceased
- 1994-10-07 ZA ZA947879A patent/ZA947879B/en unknown
-
1996
- 1996-04-04 KR KR1019960701794A patent/KR960704829A/en not_active Application Discontinuation
- 1996-04-09 FI FI961553A patent/FI961553A/en not_active Application Discontinuation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086858A (en) * | 2012-12-30 | 2013-05-08 | 浙江工业大学 | Synthetic method of 3-methyl-cyclopentanone |
| CN112010744A (en) * | 2019-05-29 | 2020-12-01 | 武汉臻智生物科技有限公司 | Farnesyl acetone and preparation method thereof |
| CN110981710A (en) * | 2019-11-26 | 2020-04-10 | 万华化学集团股份有限公司 | Method for synthesizing methyl heptenone from isoprene |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2710908A1 (en) | 1995-04-14 |
| FI961553A0 (en) | 1996-04-09 |
| EP0722432A1 (en) | 1996-07-24 |
| FI961553A (en) | 1996-04-09 |
| IL111166A0 (en) | 1994-12-29 |
| ZA947879B (en) | 1995-05-22 |
| AU7995894A (en) | 1995-05-01 |
| AU675367B2 (en) | 1997-01-30 |
| FR2710908B1 (en) | 1995-11-17 |
| WO1995009830A1 (en) | 1995-04-13 |
| BR9407734A (en) | 1997-02-12 |
| CA2173618A1 (en) | 1995-04-13 |
| JPH09503219A (en) | 1997-03-31 |
| KR960704829A (en) | 1996-10-09 |
| HUT74481A (en) | 1997-01-28 |
| CZ100796A3 (en) | 1996-07-17 |
| HU9600905D0 (en) | 1996-05-28 |
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